Thermodynamics of Solutions with Physical and Chemical Interactions. Solubility of Acetylene in Organic Solvents

Abstract

A set of thermodynamically consistent equations has been developed for representing the properties of solvating binary liquid mixtures. Chemical interactions between solute and solvent are taken into account by K, an equilibrium constant for complex formation; physical forces between solute, solvent, and complex are represented by van Laar equations through a single physical interaction parameter, a. Solution of the resulting equations by iterative techniques for typical, physically significant values of K and a demonstrates that a wide range of mixture behavior can be represented. Literature data for solubility of acetylene in a variety of solvents have been analyzed and best values of K and a are reported for 13 solvents. The new set of equations give a better fit of the data than that obtained using common two-parameter equations for the excess Gibbs energy, The method developed here can be extended to a variety of cases with strong specific interactions; it provides a basis for general treatment of strongly nonideal liquid mixtures.

Stereoselectivities and reaction rates in Diels-Alder reactions promoted by non-aqueous solvents and their aqueous mixtures: Correlations with non-adjustable parameters

“…Equations (8), (10) and (12), representing log(kN/k,), log(N/X) and log k,,, respectively, were tested against reactions with the corresponding experimental data. In Table 1 are recorded the values of Int.…”

“…from an analysis of the experimental rate data for a reaction. Equation (8) is an operational expression yielding a linear plot between log(kN/kx) and Q for a given reaction in different solvents.…”

Molecular Interactions in Tri-n-butyl Phosphate−Diluent Mixtures

“…Our model is similar to the Harris and Prausnitz (1969) model if (1) only the AB complex is allowed, (2) both A and B monomers are the same size, and (3) j ) 1. In this case we only have chemical and regular solution term contributions to g E .…”

Modelling the fluid phase behaviour of aqueous mixtures of multifunctional alkanolamines and carbon dioxide using transferable parameters with the SAFT-VR approach

“…From a seemingly diametric physical standpoint, originally attributed to van Laar 16,17 and his followers, the existence of any molecular species other than the unreacted components is denied, and the properties of the mixture are attributed to large differences in the intermolecular interactions between the species which may lead to aggregation. While the opposing chemical and physical perspectives to dealing with reactive mixtures led to "harsh polemic" from the very beginning 18 , it is now recognized that the Dolezalek and van Laar views are but extreme representations of the actual situation: the distinction between chemical and physical forces is often arbitrary and in many cases the designation of a mixture as "chemical" or "physical" is only a matter of taste or convenience 19 . It is reasonable to assume that a physical treatment is appropriate when the "reactions" do not lead to species which are very different chemically, particularly in the case of reversible reactions, but of course this will not be the case when the products are significantly distinct from the reactants.…”